Water stable copper paddlewheel metal organic framework (mof) compositions and processes using the mofs

ABSTRACT

This invention relates to a Cu-BTC MOF which is water stable. The Cu-BTC MOF has open coordination sites and has been post synthesis modified by partially occupying the open sites with a ligand such as acetonitrile (CH 3 CN). The resultant MOF retains at least 40% of its as synthesized surface area after exposure to liquid water at 60° C. for 6 hours. This is an unexpected result versus the MOF which has not been post treated with ligands such as acetonitrile. This MOF can be used to abate contaminants such as ammonia in gas streams and especially air streams.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority from provisional application62/887,421, filed Aug. 15, 2019, incorporated herein in its entirety.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

This invention was made with U.S. Government support under Agreement No.W15QKN-18-9-1004 awarded by the ACC-NJ to the CWMD Consortium. TheGovernment has certain rights in the invention.

FIELD

This invention relates to metal organic framework (MOF) materials whichare water stable and have a high capacity for ammonia. The inventionfurther relates to methods of preparing and using the MOF materials.

BACKGROUND

Purification of various gaseous stream is important for variousapplications such as semiconductor manufacture. Additionally, variousstreams can contain contaminants which can affect the performance of thedesired stream. One such compound is ammonia. Ammonia can be present innatural gas streams and must be removed. Ammonia is also toxic to humansand because of its availability can be used as a chemical warfare agent.Thus, there is a need for materials which can sequester or removeammonia from various gaseous streams.

One class of compounds which has been identified as being capable ofremoving ammonia are metal organic framework (MOF) materials. MOFs areporous materials comprised of inorganic metal nodes, linked together byat least bidentate organic ligands with capabilities for gas storage.The various combinations of metals and organic linkers allow for tuningof their physical and chemical properties.

HKUST-1 (Hong Kong University of Science and Technology), also known asCu-BTC, Cu₃(BTC)₂, MOF-199 is a copper based MOF, in which paddlewheelCu-dimers are linked together by 1,3,5 benzenetricarboxylic acid (BTC)to form a 3-dimensional pore structure. Cu-BTC has been shown to besuperior to other MOFs for the adsorption of basic gases such asammonia, due to coordinatively unsaturated Cu-sites. However, Cu-BTC isnot water stable losing its porosity and ammonia uptake capacity alongwith degradation or collapse of its crystalline structure. Thus, Cu-BTCin its powder form is not a viable material for this application.Attempts have been made to make Cu-BTC more water stable. There is onereport (Jared B. DeCoste et. al., J. Chemical Science, 2016,7,2711)showing that Cu-BTC when incorporated into a mixed matrix membrane hassubstantially increased water stability versus the as synthesizedCu-BTC. Although the Cu-BTC/MMM combination has increased waterstability, it has the limitation that it can only be used as a membraneand reduces the effective mass of the MOF which is accessible. Anothermethod used to stabilize Cu-BTC is perfluoro alkane plasma treatment,but this treatment reduces the surface area of the Cu-BTC and is verydifficult to carry out especially on a large scale. Perfluoro alkanesare also an environmental concern. Accordingly, there still exists aneed for a water stable MOF with good ammonia capacity.

Applicants have discovered that Cu-BTC can be made water stable whilemaintaining its high capacity for ammonia by substituting some of theBTC ligand with 5-aminoisophthatlic acid (AIA). Applicants have alsofound that taking a Cu-BTC MOF and solvating it with CH₃CN(acetonitrile) followed by activation provides a MOF with greatlyimproved water stability.

SUMMARY OF THE INVENTION

One embodiment of the invention is a metal organic framework (MOF)composition comprising a coordination product of a copper metal ion anda mixture of organic ligands selected from 1,3,5-benzenetricarboxylicacid (BTC) and 5-aminoisophthalic acid (AIA). The produced MOF will bereferred to herein as Cu-BTC-AIA MOF. The Cu-BTC-AIA MOF ischaracterized in that it retains at least 40% of its as synthesizedsurface area after exposure to water at 60° C. for 24 hours. TheCu-BTC-AIA MOF also reacts with or has sorptive affinity for toxic gasesselected from ammonia, hydrogen sulfide, hydrogen cyanide, cyanogenchloride, chlorine, nitrogen dioxide, hydrazine, arsine, phosgene,phosphine, and boron trifluoride.

In another embodiment the Cu-BTC/AIA MOF has an as synthesizedBrunauer-Emmett-Teller (BET) surface area of at least 1200 or 1300 or1400 or 1500 or 1600 or 1700 or 1800 m²/g.

In a further embodiment the molar ratio of BTC:AIA in the MOF variesfrom about 99:1 to about 1:99.

In yet another embodiment the Cu-BTC-AIA MOF retains at least 50%, or atleast 60%, or at least 70%, or at least 80% of its surface area afterexposure to water at 60° C. for 6 hours

In yet another embodiment the Cu-BTC-AIA MOF retains at least 40%, or atleast 50%, or at least 60%, or at least 70% of its surface area afterexposure to water at 60° C. for 24 hours.

In still another embodiment the CU-BTC-AIA MOF is formed into a shapedbody selected from pellets, spheres, disks, monolithic body, irregularlyshaped particles, extrudates, and mixtures thereof.

In yet another embodiment the Cu-BTC-AIA MOF is deposited as a layer ona support selected from a monolith, spherical support, ceramic foam,woven fabrics, nonwoven fabrics, membranes, pellets, extrudates,irregularly shaped particles, and mixtures thereof.

In a further embodiment the Cu-BTC-AIA MOF has dispersed thereon atleast one catalytic metal selected from zinc, nickel, palladium,platinum, copper, molybdenum, iron, vanadium, manganese, and rhodium.

Yet another embodiment is a process for purifying a gaseous streamcomprising a contaminant

the process comprising contacting the gaseous stream with a) acoordination product of a copper metal ion and a mixture of organicligands selected from 1,3,5-benzenetricarboxylic acid (BTC) and5-aminoisophthalic acid (AIA) the Cu-BTC-AIA MOF, the MOF characterizedin that it it retains at least 40% of its as synthesized surface areaafter exposure to water at 60° C. for 24 hours, or b) a MOF which is acoordination product of a copper metal ion and1,3,5-benzenetricarboxylic acid (BTC) ligand the MOF characterized inthat the copper has open coordination sites which are at least partiallyoccupied by acetonitrile (CH₃CN) (CH₃CN-CuBTC to at least partiallyremove the contaminant from the gaseous stream and provide a purifiedgaseous stream.

Another embodiment is where the contaminant is selected from ammonia,hydrogen sulfide, hydrogen cyanide, cyanogen chloride, chlorine,nitrogen dioxide, hydrazine, arsine, phosgene, phosphine, borontrifluoride, and mixtures thereof.

A specific embodiment is where the contaminant is ammonia and thegaseous stream is air.

Another embodiment is a process for preparing a metal organic framework(MOF) composition comprising:

-   -   1) admixing a copper compound with 1,3,5-benzenetricarboxylic        acid (BTC) and a solvent to provide a first mixture;    -   2) heating the first mixture to a temperature of about 25° C. to        about 100° C.;    -   3) adding 5-aminoisophthalic acid (AIA) and reacting the        resulting second mixture for a time sufficient to provide the        MOF; and    -   4) isolating the MOF in the form of a powder.

A still further embodiment is a metal organic framework (MOF)composition comprising: a coordination product of a copper metal ion and1,3,5-benzenetricarboxylic acid (BTC) ligand the MOF characterized inthat the copper has open coordination sites which are at least partiallyoccupied, i.e. exchanged, by an alkyl or aromatic nitrile, a cyclicamine or mixtures thereof. An example of an alkyl nitrile isacetonitrile (CH₃CN) (herein referred to as CH₃CN-Cu-BTC). An example ofa cyclic amine is pyridine (herein after referred to asPyridine-Cu-BTC). Generally, the alkyl nitrile, aromatic nitrile, cyclicamine or mixture thereof exchanged MOFs are characterized in that theyare water stable as shown by their ability to retain a high percentageof their as synthesized surface area after exposure to liquid water atroom temperature for 24 hours. Specifically, the CH₃CN-Cu-BTC retains atleast 40% of its as synthesized surface area after exposure to liquidwater at room temperature for 24 hours.

Yet another embodiment is a CH₃CN-Cu-BTC MOF material having an assynthesized Brunauer-Emmett-Teller (BET) surface area of at least 1200m²/g.

A further embodiment is a CH₃CN-Cu-BTC MOF material having a gravimetricuptake capacity for ammonia of at least 0.2 g of ammonia per gram of MOFmeasured at 675 torr and 25° C.

A still further embodiment is a CH₃CN-Cu-BTC MOF material having a porevolume of at least 0.5 cc/g.

These and other objects and embodiments will become more evident after adetailed description of the invention.

DETAILED DESCRIPTION OF THE INVENTION

Ammonia is one of the most widely manufactured chemicals with uses inthe production of fertilizers. Ammonia is also toxic to humans andbecause of its wide availability can be used as a chemical warfareagent. This has created a need for materials which can effectivelyremove ammonia from various gaseous streams such as air. Metal organicframework materials (MOF) are microporous materials with high surfaceareas which are capable of adsorbing molecules in the internal pores ofthe structure. One MOF which has been found to have a high capacity forammonia is HKUNST-1, also known as Cu-BTC or Cu₃(BTC)₂, where BTC isbenzene 1,3,5-tricarboxylate. Cu-BTC is a copper based MOF, in whichpaddlewheel Cu-dimers are linked together by benzene1,3,5-tricarboxylate to form a 3-dimensional pore structure.

However, Cu-BTC is extremely water sensitive and thus not very usefulfor ammonia capture. Applicants have discovered that Cu-BTC can be madewater stable my either synthesizing the MOF using a mixture of ligandsor “capping” the copper atoms. By capping is meant that a molecule iscoordinatively bonded to open sites of the copper atom.

Thus, one aspect of the invention is replacing some of the BTC with5-aminoisophthalic acid (AIA). The molar ratio of BTC to AIA can rangefrom about 1:99 to about 99:1, or about 10:90 to about 90:10, or about30:70 to about 70:30, or about 40:60 to about 60:40. Specific ratiosinclude BTC:AIA of about 50:50 (or 1:1), 25:75(or 1:3), 75:25 (or 3:1),20:40 (or 1:2) and 40:20 (or 2:1).

The synthesis of Cu-BTC (HKUST-1) was reported by S.S.Y. Chui et. al,Science, 1999, vol.283, 1148. The synthesis involves reacting a coppersalt (cupric nitrate) with BTC in a water ethanol mixture at 180° C. for12 hours under pressure. In one aspect the synthesis developed by theinventors involves mixing a copper compound selected from cupricnitrate, copper chloride, copper acetate, and copper sulfate with 1,3,5,benzenetricarboxylic acid (BTC) and 5-aminoisophthalic acid (AIA). Inthe description which follows the copper nitrate is used as theexemplary copper compound, but the invention is not limited to coppernitrate.

The amount of BTC and AIA present in the reaction mixture is such toprovide the molar ratios set forth above. The solvent may comprise,water and dimethylformamide (DMF). Optionally, the solvent mayadditionally contain ethanol and/or nitric acid. The volumetric ratio ofwater to DMF varies from about 99:1, or from 1:99. When ethanol is alsopresent, the volumetric ratio of water to ethanol is from about 99:1 toabout 1:99. The reaction mixture can be prepared in a number of ways.For example, BTC can be dissolved in DMF, then the copper nitrate andwater are added, followed by heating to the desired temperature andaddition of the desired AIA once the desired temperature is achieved. Asecond way to prepare the reaction mixture is to dissolve the BTC inethanol, then add copper nitrate plus water and DMF, heat the mixture tothe desired temperature and then add the AIA. A third way to prepare thereaction mixture is to mix the BTC with DMF and water, heat to desiredtemperature, add copper nitrate followed by AIA. A fourth way to preparethe reaction mixture is to mix the BTC with the DMF and water, heat todesired temperature, add the copper nitrate and nitric acid. The AIA maybe added all at once or may be added continuously over a time periodfrom about 5 minutes to about 480 minutes. Applicants have found thatadding the AIA continuously over a set period of time provides a MOFwith better properties, e.g. increased surface area. Regardless m²/g ofhow the reaction mixture is prepared, it is heated to a temperature fromabout 25° C. to about 120° C. or from about 25° C. to about 100° C., orfrom about 25° C. to about 75° C. or from about 25° C. to about 50° C.The reaction mixtures is maintained at the desired temperature for atime from about 12to about 48 or from about 12 to about 24. Theresulting MOF is isolated by filtration, washed with methanol and thendried at a temperature from about 75° C. to about 150° C. for about 8 toabout 72 hours under vacuum.

The Cu-BTC-AIA MOF of the invention is characterized by aBrunauer-Emmett-Teller (BET) surface area of at least 1200 m²/g or atleast 1300 m²/g or at least 1400 m²/g or at least 1500 m²/g or at least1600 m²/g or at least 1700 m²/g or at least 1800 m²/g. Morespecifically, the MOF has a surface area from about 1300 m²/g to about2000 m²/g or from about 1500 m²/g to about 1900 m²/g. The MOF also has agravimetric uptake capacity for ammonia of at least 0.20 g of ammoniaper gram of MOF measured at 650 torr and 25° C. More specifically theammonia capacity varies from about 0.20 g to about 0.45 g of ammonia pergram of MOF or from about 0.20 g to about 0.40 g of ammonia per gram ofMOF.

The Cu-BTC-AIA MOF of the invention is also characterized in that itcrystallizes as blue rectangular crystals.

An important feature of the Cu-BTC-AIA of the invention is that it hasmuch improved stability when exposed to water. For example, when theCu-BTC-AIA MOF is exposed to water at 60° C. for 24 hours, it maintainsat least 40% of its as synthesized surface area, or at least about 50%or at least about 70%, or at least about 80% of its as synthesizedsurface area. This water stability test is an extreme test which veryfew MOFs are able to pass. In fact, it has been reported in theliterature that Cu-BTC MOF when exposed to 90% relative humidity air at25° C. loses a considerable amount of its porosity and ammonia capacityand becomes amorphous.

Along with maintaining its surface area, the Cu-BTC-AIA of the inventionalso maintains its capacity for ammonia uptake. After exposure to waterat 60° C. for 24 hours. the MOF of the invention retains at least 40% ofits ammonia capacity, or at least 50%, or at least 70% or at least 90%of its ammonia capacity.

Another characteristic of the Cu-BTC-AIA is that it has a pore volume ofat least 0.45 cc/g or

0.6 cc/g, or 0.7cc/g. At least 50% of the pore volume is retained afterexposure to water at 60° C. for 24 hours.

Another aspect of the invention is a Cu-BTC which has been made waterstable by a post synthesis modification. In this case the Cu-BTC isprepared by means well know in the art such as that described by S.S.Y.Chui et. al cited above. Once synthesized, isolated, and dried theCu-BTC MOF is contacted with a ligand which is more strongly bonded tothe copper atom than water but less strongly than ammonia. These ligandsinclude alkyl nitrile, aromatic nitriles, cyclic amines and mixturesthereof. Specific examples are acetonitrile (CH₃CN), pyridine, andmixtures thereof. Acetonitrile is particularly advantageous and will beuse as the exemplary ligand hereafter. However, it is understood thatthe invention is not limited to acetonitrile. The Cu-BTC is exchangedwith acetonitrile by soaking the MOF in acetonitrile for a period oftime from about 5 hours to about 20 hours. At the end of the contactperiod, the MOF material is isolated and then activated at temperaturesof about 30° C. to about 70° C. under vacuum for a time from 30 min to150 min. Activation can be carried out at temperatures of about 40° C.to about 60° C. for a time of about 60 min to about 120 min ortemperatures of about 45° C. to about 55° C. for a time of about 80 minto about 100 min or a temperature of about 50° C. for a time of about 90minutes. This MOF (herein after CH₃CN-Cu-BTC) is characterized in thatit has much improved stability when exposed to water. For example, whenthe CH₃CN-Cu-BTC MOF is exposed to water at room temperature for sixhours, it maintains at least 40% of its as synthesized surface area, orat least about 50% or at least about 70%, or at least about 90% of itsas synthesized surface area.

The CH₃CN-Cu-BTC also has a high ammonia capacity similar to Cu-BTC. Thecapacity is at least 0.3 gram of ammonia per gram of MOF.

Although the MOF materials of the invention can be used in the powderform, it advantageous to form the MOF materials into various shapedbodies such as pellets, spheres, disks, monolithic bodies, irregularlyshaped particles and extrudates. The methods of forming these types ofshapes are well known in the art. The MOF materials can be formed intovarious shapes by themselves or using a binder. When selecting a binder,it is important to select a binder such that the surface area andammonia capacity is not adversely affected once the desired shaped bodyis formed. Materials which can be used as binders include withoutlimitation cellulose, silica, carbon, alumina, and mixtures thereof.

The forming process usually involves preparing a thick paste-likematerial by mixing the MOF materials with a solvent or a binder and asolvent. Once the paste-like material is formed it can be extrudedthrough a die having holes of about 1-2 mm to form extrudates of varyinglength, e.g. 6-10 mm. The paste or even the powder itself can be pressedat high pressure to form pellets or pills. Other means of forming shapesinclude pressure molding, metal forming, pelletizing, granulation,extrusion, rolling methods and marumerizing.

Another aspect of the invention involves depositing a catalytic metalonto the shaped MOF body. The catalytic metal may be chosen from zinc,copper, nickel, chromium, molybdenum, tungsten, niobium, rhenium,vanadium, silver, platinum, palladium, rhodium, iridium, and mixturesthereof. Deposition of a catalytic metal onto the shaped MOF support iscarried out by conventional means which usually involve taking asolution containing a compound of the desired metal and impregnating theshaped MOF body with it, followed by drying and optional treatments suchas calcination, and/or reduction.

In yet another aspect of the invention, the MOF materials can bedeposited onto articles such as, but not limited to, monolith, sphericalsupport, ceramic foam, woven fabrics, nonwoven fabrics, membranes,pellets, extrudates, irregularly shaped particles, and mixtures thereof.When the desired article is a monolith, spherical support, ceramic foam,pellets, extrudates, irregularly shaped particles, a slurry of the MOFmaterial is prepared and deposited on the article by means such asdipping, spray drying, etc. followed by drying and optionallycalcination. For membranes it is possible to form the MOF materialdirectly on the membrane. The MOF materials of the invention can bedeposited or dispersed onto fabrics (woven and non-woven) or polymers bytechniques such as electro-spinning, direct crystal growth, and layer bylayer deposition.

The MOF materials of the invention have many uses such as purifying agaseous stream, especially an air stream, which contains ammonia. Theprocess involves placing the MOF material into a vessel through whichthe gas stream is flowed through thereby substantially removing theammonia from the stream. One particular type of purification device is agas mask wherein the MOF materials of the invention are placed within acartridge which is part of the mask and through which air passesthrough. The MOF in the mask can adsorb the ammonia and allow the maskwearer to breathe for a period of time before the ammonia breaksthrough. Such a device is described in U.S. Ser. No. 10/272,279 which isincorporated by reference in its entirety.

EXAMPLES Examples 1-5

A series of experiments were conducted in which varying amounts of AIAwere incorporated into a Cu-BTC MOF. The parameters used for eachexperiment are presented in Table 1. The general procedure involveddissolving the BTC in ethanol (when no DMF was used) or DMF (when onlyDMF and water was used or DMF and ethanol was used). Once the BTC isdissolved, copper nitrate and the remaining solvents, e.g. water orwater plus ethanol, are added and the reaction mixture was heated to thedesired temperature, at which time the AIA was added, and the finalreaction mixture was reacted for the desired amount of time. If nitricacid was added, it was added at the same time as the AIA. The resultingMOF powder was then isolated by filtration, washed with methanol andthen dried at 150° C. for 12 hours.

TABLE 1 Effect of Various Parameters on Cu-BTC-AIA MOF Synthesis DosingReaction Reaction Ex. BTC AIA Cu(NO₃)₂ DMF Water ETOH HNO₃ AIA Rate TimeTemp. No. (g) (g) (g) (L) (L) (L) (L) Dosing (mL/min) (hrs.) (° C.) 113.5 5.8 22.4 0.50 0.50 0.0 0.002 No N/A 24 90 2 13.5 5.8 22.4 0.50 0.500.0 0.0 No N/A 24 90 3 13.5 5.8 22.4 0.04 0.48 0.48 0.0 No N/A 24 75 46.7 5.8 22.4 0.50 0.50 0.0 0.0 Yes 0.33 24 90 5 9.0 3.9 22.4 0.50 0.500.0 0.0 No N/A 24 90

Samples from the examples above were activated under vacuum at 150° C.for 12 hours and examined for their surface area, pore volume andammonia uptake before and after water treatment. Water treatment wasconducted by placing an activated sample of each MOF into a vial ofwater and then heating the vial at 60° C. for 24 hours. Surface area(BET), pore volume and ammonia uptake (at 675 torr and 25° C.). Theresults are presented in Table 2.

TABLE 2 Characterization of Cu-BTC-AIA MOFs As Synthesized After WaterTreatment Surface Surface Example Area Pore NH3 Area Pore No. (m2/g)Volume Capacity (m2/g) Volume 1 1820 0.75 0.4 1670 0.70 2 1833 0.76 0.41626 0.67 3 1497 0.65 0.35 1056 0.45 4 1190 0.49 0.28 724 0.31 5 16860.70 0.40 1083 0.46

Example 6

Cu-BTC was prepared by solvothermal reaction of BTC with copper nitrate.The resulting Cu-BTC was washed with methanol and then soaked inacetonitrile for 18 hours. During this time the acetonitrile wasreplaced with fresh acetonitrile two times. The CH₃CN-Cu-BTC wasisolated and one portion of the product was activated in vacuum at 50°C. for 90 minutes. A portion of this activated CH₃CN-Cu-BTC was immersedin water for one day and compared to a sample of Cu-BTC. TheCH₃CN-Cu-BTC sample retained its crystalline appearance, as determinedby optical microscope, whereas the Cu-BTC sample showed the presence ofmostly amorphous material.

1. A metal organic framework (MOF) composition comprising: acoordination product of a copper metal ion and1,3,5-benzenetricarboxylic acid (BTC) ligand the MOF characterized inthat the copper has open coordination sites which are at least partiallyoccupied by acetonitrile (CH₃CN) and it retains at least 40% of its assynthesized surface area after exposure to liquid water at roomtemperature for 6 hours.
 2. The composition of claim 1 furthercharacterized in that the MOF has an as synthesizedBrunauer-Emmett-Teller (BET) surface area of at least 1200 m²/g.
 3. Thecomposition of claim 1 further characterized in that the MOF has agravimetric uptake capacity for ammonia of at least 0.3 g of ammonia pergram of MOF measured at 675 torr and 25° C.
 4. The MOF of claim 1further characterized in that the MOF has a pore volume of at least 0.5cc/g.
 5. The MOF of claim 1 where the MOF retains at least 50% of itssynthesized surface area after exposure to liquid water at roomtemperature for 6 hours.
 6. The MOF of claim 1 further characterized inthat the MOF is formed into a shaped body selected from pellets,spheres, disks, monolithic body, irregularly shaped particles,extrudates, and mixtures thereof.
 7. The MOF of claim 1 furthercharacterized in that the MOF is deposited as a layer on a supportselected from a monolith, spherical support, ceramic foam, wovenfabrics, nonwoven fabrics, membranes, pellets, extrudates, irregularlyshaped particles, and mixtures thereof.
 8. The MOF of claim 1 furthercharacterized in that the MOF has dispersed thereon at least onecatalytic metal selected from zinc, copper, nickel, chromium,molybdenum, tungsten, niobium, rhenium, vanadium, silver, platinum,palladium, rhodium, iridium, and mixtures thereof.
 9. A process forpurifying a gaseous stream: the process comprising contacting thegaseous stream comprising a at least one contaminant selected fromammonia, hydrogen sulfide, hydrogen cyanide, cyanogen chloride,chlorine, nitrogen dioxide, hydrazine, arsine, phosgene, phosphine, andboron trifluoride with a metal organic framework material (MOF) which isa coordination product of a copper metal ion and1,3,5-benzenetricarboxylic acid (BTC) ligand the MOF characterized inthat the copper has open coordination sites which are at least partiallyoccupied by acetonitrile (CH₃CN) (CH₃CN-CuBTC), to at least partiallyremove the contaminant from the gaseous stream and provide a purifiedgaseous stream.
 10. The process of claim 9 where the gaseous stream isan air stream and the contaminant is ammonia.
 11. The process of claim 9where at least 75% of the ammonia in the gaseous stream is removed. 12.The process of claim 9 where the MOF is deposited as a layer on asupport selected from a monolith, spherical support, ceramic foam, wovenfabrics, nonwoven fabrics, membranes, pellets, extrudates, irregularlyshaped particles, and mixtures thereof.
 13. The process of claim 12where the support is a woven fabric or nonwoven fabric.
 14. The processof claim 9 where the MOF is formed into a shaped body selected frompellets, spheres, disks, monolithic body, irregularly shaped particles,extrudates, and mixtures thereof.
 15. The process of claim 14 where theshaped body is provided in a bed through which the gaseous stream flowsthrough.